U.S. patent number 4,600,761 [Application Number 06/782,571] was granted by the patent office on 1986-07-15 for acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein.
This patent grant is currently assigned to Alco Chemical Corporation. Invention is credited to Charles G. Ruffner, John M. Wilkerson, III.
United States Patent |
4,600,761 |
Ruffner , et al. |
July 15, 1986 |
**Please see images for:
( Certificate of Correction ) ** |
Acrylic emulsion copolymers for thickening aqueous systems and
copolymerizable surfactant monomers for use therein
Abstract
Acrylic emulsion copolymers are prepared by emulsion
polymerization of (A) a surfactant monomer, (B) an .alpha.,
.beta.-ethylenically unsaturated carboxylic acid monomer, (C) a
nonionic .alpha., .beta.-ethylenically unsaturated monomer and (D)
optionally a polyethylenically unsaturated cross-linking monomer.
The surfactant monomer is prepared by condensing a polyhydric
alcohol or primary amine-containing nonionic surfactant with a
monoethylenically unsaturated monoisocyanate. At a low pH the
copolymer may be in the form of an aqueous dispersion or latex, but
thickens upon neutralization of at least some of the carboxyl
groups.
Inventors: |
Ruffner; Charles G. (Hamilton
County, TN), Wilkerson, III; John M. (Hamilton County,
TN) |
Assignee: |
Alco Chemical Corporation
(Chattanooga, TN)
|
Family
ID: |
27110137 |
Appl.
No.: |
06/782,571 |
Filed: |
October 1, 1985 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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719768 |
Apr 4, 1985 |
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Current U.S.
Class: |
526/270; 524/549;
524/555; 549/476; 507/120; 526/301 |
Current CPC
Class: |
C08F
220/04 (20130101); C08F 222/20 (20130101); C08F
246/00 (20130101); C08G 18/8108 (20130101); C09D
7/43 (20180101); C09K 3/00 (20130101); C09K
8/24 (20130101); C11D 3/3765 (20130101); D06P
1/525 (20130101); D21H 19/58 (20130101); C08L
33/02 (20130101); C08L 33/08 (20130101); C08L
39/00 (20130101) |
Current International
Class: |
C09D
7/00 (20060101); C09K 8/02 (20060101); C09K
8/24 (20060101); C11D 3/37 (20060101); D21H
19/58 (20060101); D21H 19/00 (20060101); D06P
1/52 (20060101); D06P 1/44 (20060101); C08F
222/20 (20060101); C08F 222/00 (20060101); C08G
18/00 (20060101); C08F 220/04 (20060101); C08F
220/00 (20060101); C08F 246/00 (20060101); C08G
18/81 (20060101); C11D 17/00 (20060101); C09K
3/00 (20060101); C08F 216/14 () |
Field of
Search: |
;526/270,301,302
;524/555 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Specialty Chemicals Developmental Products Technical
Data-Developmental Monomer XAS-10743.00 Isocyanatoethyl
Methacrylate, The Dow Chemical Co. (1983). .
IEM Isocyanatoethyl Methacrylate A New Difunctional
Monomer-Properties, Applications, and Safe Handling, The Dow
Chemical Co. (1984). .
Paul E. Cranley "Isocyanatoethyl Methacrylate: A Latent Crosslinker
for Coating and Adhesive Resins:, The Dow Chemical Co. (1983).
.
IEM Dual Functional Monomer, The Dow Chemical Co. (1983). .
Research Disclosure 20816 (Aug. 1981)..
|
Primary Examiner: Michl; Paul R.
Attorney, Agent or Firm: Howson and Howson
Parent Case Text
BACKGROUND OF THE INVENTION
This application is a continuation-in-part of Ser. No. 719,768
filed Apr. 4, 1985.
Claims
I claim:
1. A copolymer obtained by aqueous emulsion copolymerization of a
monomer system comprising
(A) about 1 to about 25 percent of at least one nonionic urethane
monomer which is the urethane reaction product of a
monoethylenically unsaturated monoisocyanate with a nonionic
surfactant of the formula: ##STR15## in which x is an integer of
from 1 to 150 and y is an integer of from 0 to 40 when R a sorbitan
fatty ester of the formula ##STR16## where each of p, q, r and s is
an integer and the sum of said integers is from 0 to 100, R.sub.1
is H or --COR.sub.2 and R.sub.2 is alkyl, alkylphenyl, or
dialkylphenyl 5 to 30 carbon atoms; or x and y are each integers of
from 0 to 40 when R is --NH(CH.sub.2).sub.3 O--R.sub.3, or
##STR17## where R.sub.2 is H or R.sub.3, and R.sub.3 is alkyl,
alkylphenyl, or dialkylphenyl of from 5 to 30 carbon atoms;
(B) about 5 to about 70 percent of a copolymerizable
.alpha.,.beta.-ethylenically unsaturated carboxylic acid monomer of
the formula ##STR18## where R is H and R.sub.1 is H, an alkyl group
containing from 1 to 4 carbon atoms, or --CH.sub.2 COOX; R is
--COOX and R.sub.1 is H, and X is H or an alkyl group containing
from 1 to 4 carbon atoms,
(C) about 10 to to about 90 percent of at least one nonionic,
copolymerizable .alpha.,.beta.-ethylenically unsaturated monomer of
the formula
where Y is H and Z is CN, Cl, --COOR, C.sub.6 H.sub.4 R, ##STR19##
or --CH.dbd.CH.sub.2 ; Y and Z are Cl, and Y is CH.sub.3 and Z is
CN, ##STR20## --CH.dbd.CH.sub.2, --C.sub.6 H.sub.4 R, or
--COOR.sub.1, and R is H, Cl, Br or alkyl containing from 1 to 4
carbon atoms; R.sub.1 is alkyl containing from 1 to 12 carbon
atoms, or hydroxyalkyl containing from 2 to 8 carbon atoms, and
R.sub.2 is alkyl containing from 1 to 8 carbon atoms; and
(D) up to 1 percent of a copolymerizable polyethylenically
unsaturated cross-linking monomer, said percentages being by
weight, based on the total weight of said monomers.
2. An emulsion copolymer according to claim 1 polymerized from a
monomer system comprising
(A) about 5 to about 15 percent of said nonionic urethane
monomer,
(B) about 30 to about 50 percent of said
.alpha.,.beta.-ethylenically unsaturated monomer in which R is H,
and R.sub.1 is H or an alkyl group containing from 1 to 4 carbon
atoms, and
(C) about 30 to about 70 percent of said
.alpha.,.beta.-ethylenically unsaturated monomer in which Y is H
and Z is --COOR where R is alkyl containing from 1 to 4 carbon
atoms.
3. An emulsion copolymer according to claim 2 in which in said
nonionic urethane monomer (A), R is a sorbitan monoester in which
R.sub.1 is an alkyl group containing from 10 to 20 carbon atoms and
the sum of p, q, r and s is 10 to 20, and x and y are zero.
4. An emulsion coploymer according to claim 3 in which in said
nonionic urethane monomer (A), R is sorbitan trioleate, and the sum
of p, q, r and s is zero.
5. An emulsion copolymer according to claim 2 in which in said
nonionic urethane monomer (A), R is --N(R.sub.3).sub.2 where
R.sub.3 is an alkyl group containing from 5 to 15 carbon atoms, x
is an integer of from 2 to 20 and y is zero.
6. A copolymer obtained by aqueous emulsion copolymerization of a
monomer system comprising
(A) about 1 to about 25 percent of at least one substituted
carbonyl amino alkyl acrylate monomer of the formula: ##STR21## in
which A is an alkylene group of the formula (CH.sub.2).sub.n where
n is an integer of from 2 to 20; Z is CH.sub.2 .dbd.CH--, CH.sub.2
.dbd.C(CH.sub.3)--, CH.sub.2 .dbd.C(Cl)--, CH.sub.3 CH.dbd.CH--, or
##STR22## x is an integer of from 1 to 150 and y is an integer of
from 0 to 40 when R a sorbitan fatty ester of the formula ##STR23##
where each of p, q, r and s is an integer and the sum of said
integers is from 0 to 100, R.sub.1 is H or --COR.sub.2 and R.sub.2
is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon
atoms; or x and y are each integers of from 0 to 40 when R is
--NH(CH.sub.2).sub.3 O--R.sub.3, or ##STR24## where R.sub.2 is H or
R.sub.3, and R.sub.3 is alkyl, alkylphenyl, or dialkylphenyl of
from 5 to 30 carbon atoms;
(B) about 5 to about 70 percent of a copolymerizable
.alpha.,.beta.-ethylenically unsaturated carboxylic acid monomer of
the formula ##STR25## where R is H and R.sub.1 is H, an alkyl group
containing from 1 to 4 carbon atoms, or --CH.sub.2 COOX; R is
--COOX and R.sub.1 is H, and X is H or an alkyy group containing
from 1 to 4 carbon atoms,
(C) about 10 to to about 90 percent of at least one nonionic,
copolymerizable .alpha.,.beta.-ethylenically unsaturated monomer of
the formula
where Y is H and Z is CN, Cl, --COOR, --C.sub.6 H.sub.4 R,
##STR26## or --CH.dbd.CH.sub.2 ; Y and Z are Cl, and Y is CH.sub.3
and Z is CN, ##STR27## --CH.dbd.CH.sub.2, --C.sub.6 H.sub.4 R, or
--COOR.sub.1, and R is H, Cl, Br or alkyl containing from 1 to 4
carbon atoms; R.sub.1 is alkyl containing from 1 to 12 carbon
atoms, or hydroxyalkyl containing from 2 to 8 carbon atoms, and
R.sub.2 is alkyl containing from 1 to 8 carbon atoms; and
(D) up to 1 percent of a copolymerizable polyethylenically
unsaturated cross-linking monomer, said percentages being by
weight, based on the total weight of said monomers.
7. An emulsion copolymer according to claim 6 polymerized from a
monomer system comprising
(A) about 5 to about 15 percent of said substituted carbonyl amino
alkyl acrylate monomer,
(B) about 30 to about 50 percent of said
.alpha.,.beta.-ethylenically unsaturated monomer in which R is H,
and R.sub.1 is H or an alkyl group containing from 1 to 4 carbon
atoms, and
(C) about 30 to about 70 percent of said
.alpha.,.beta.-ethylenically unsaturated monomer in which Y is H
and Z is --COOR where R is alkyl containing from 1 to 4 carbon
atoms.
8. An emulsion copolymer according to claim 7 in which in said
substituted carbonyl amino alkyl acrylate monomer (A), R is a
sorbitan monoester in which R.sub.1 is an alkyl group containing
from 10 to 20 carbon atoms and the sum of p, q, r and s is 10 to
20, Z is CH.sub.2 .dbd.CH-- or CH.sub.2 .dbd.(CH.sub.3), A is
alkylene containing from 2 to 4 carbon atoms, and x and y are
zero.
9. An emulsion coploymer according to claim 8 in which in said
substituted carbonyl amine alkyl acrylate monomer (A), R is
sorbitan trioleate, and the sum of p, q, r and s is zero.
10. An emulsion copolymer according to claim 7 in which in said
substituted carbonyl amino alkyl acrylate monomer (A), R is
--N(R.sub.3).sub.2 where R.sub.3 is an alkyl group containing from
5 to 15 carbon atoms, Z is CH.sub.2 .dbd.CH or CH.sub.2
.dbd.C(CH.sub.3)--, A is alkylene containing from 2 to 4 carbon
atoms, x is an integer of from 2 to 20 and y is zero.
11. An emulsion copolymer according to claim 6 polymerized from a
monomer system comprising
(A) about 7 to about 10 percent of said substituted carbonyl amino
alkyl acrylate monomer in which Z is CH.sub.2 .dbd.C(CH.sub.3)--, A
is ethylene, x is an integer from 2 to 20 and y is zero,
(B) about 35 to about 45 percent of acrylic or methacrylic
acid,
(C) about 50 to about 60 percent of ethyl acrylate and
(D) about 0.5 to about 1 percent of said polyethylenically
unsaturated cross-linking monomer.
12. An emulsion copolymer according to claim 11 polymerized from a
monomer system comprising:
(A) a substituted carbonyl amino ethyl methacrylate selected from
the group consisting of poly(oxyethylene).sub.20 sorbitan
monooleate, and monooleyl amine-carbonyl amino ethyl
methacrylate,
(B) methacrylic acid,
(C) ethyl acrylate, and
(D) diallylphthalate.
13. An aqueous colloidal dispersion comprising from about 5 to
about 50 percent, by weight, of an emulsion copolymer of claim 6
having a pH of from about 2.5 to about 5.
14. An aqueous colloidal dispersion comprising from about 5 to
about 50 percent, by weight, of an emulsion copolymer of claim 12
having a pH of from about 2.5 to about 5.
15. A process for making the aqueous colloidal dispersion of claim
13 comprising emulsion polymerizing the monomeric system thereof at
a pH of from about 2.5 to about 5 in the presence of a free radical
producing initiator at a temperature of from about 40.degree. to
about 90.degree. C.
16. A process for making the aqueous colloidal dispersion of claim
14 comprising emulsion polymerizing the monomeric system thereof at
a pH of from about 2.5 to about 5 in the presence of a free radical
producing initiator at a temperature of from about 75.degree. to
about 85.degree. C.
17. A thickened aqueous composition containing an effective
thickening amount of at least a partially neutralized emulsion
copolymer of claim 6.
18. A process for making a thickened aqueous composition which
comprises combining with the aqueous composition an effective
thickening amount of an emulsion copolymer of claim 6 and at least
partially neutralizing said copolymer to thus thicken said
composition.
19. A thickened composition according to claim 17 comprising a
latex paint.
20. A thickened composition according to claim 17 comprising a
pigment dispersion.
21. A thickened composition according to claim 17 comprising an oil
well drilling fluid.
22. A thickened composition according to claim 17 comprising a
textile printing paste.
23. A thickened composition according to claim 17 comprising an
adhesive.
24. A thickened composition according to claim 17 comprising a
liquid detergent.
25. A thickened composition according to claim 17 comprising a
paper coating composition.
26. A thickened composition according to claim 17 comprising a wall
joint compound.
Description
Alkali soluble and alkali swellable emulsion polymers and
copolymers are well known (see e.g. U.S. Pat. Nos. 3,003,987;
3,070,561, and 3,081,198) and are useful in coatings, textile
sizings, textile printing pastes, paints and industrial coatings
where a water soluble resin can be utilized. They are also useful
as thickening agents in latex based adhesives, where clays, other
fillers, pigments and the like are present. In addition, alkali
soluble emulsion polymers and copolymers find application in
cleaners, laundry detergents, lotions, toothpastes, and other
personal care products. In petroleum exploration, acrylic polymers
are used as drilling fluid additives for viscosity control and as
bentonite extenders for enhancing performance of the drilling
fluid. Thus, according to U.S. Pat. No. 4,301,016 water soluble
alkali metal polyacrylates are useful additives in drilling fluids
based on fresh water.
A variety of natural and synthetic products based on cellulose,
starches and proteins also have found application in paints,
drilling fluids, paper coatings, adhesives, cleaners, lotions and
the like. For instance, U.S. Pat. No. 3,769,247 discloses the use
of certain cellulose ethers as thickeners for latex paints.
Although acrylic polymer emulsions offer various advantages in most
of the above-described areas of use, they have been found to be
seriously deficient in some areas, particularly in water-base paint
formulations where rheology control is essential to obtain correct
flow and leveling, and to minimize splattering and dripping from
brushes and rollers. In such paint formulations cellulose-based
thickeners generally have out-performed acrylics.
In drilling muds acrylics have performed well in fresh water
drilling, U.S. Pat. No. 4,301,016, supra, and U.S. Pat. No.
2,718,497, but acrylics have poor salt tolerance as compared to
some cellulosic materials. On the other hand acrylics and other
synthetic polymers and copolymers offer a major advantage in
manufacturing reproducability, as compared to chemically grafted or
modified natural products, provided the salt tolerance problem is
not a factor.
The resistance of acrylic polymers to biological decay is a
property which is especially beneficial in drilling muds, paints,
cleaner solutions, and personal care products. In order to provide
improved properties for specific applications, functional polymeric
side chains have been added to synthetic acrylic systems.
In various industrial applications, acrylics available as liquid
emulsions and dispersions are generally easier to use than modified
natural polymers which usually are dry powders, since the former
are capable of addition at most any point in a mixing process. On
the other hand, dry products based on starches, cellulose, and
proteins require a relatively long hydration time and take longer
to dissolve than the soluble alkali metal polymers.
Another class of acrylic based emulsion polymers, popularly known
as "inverse emulsions" and "inverse suspensions", such as those
disclosed in U.S. Pat. Nos. 3,284,393, 3,826,771, are commercially
available. These products generally rely on an organic solvent
system, typically aliphatic in nature, as the continuous phase, and
the presence of large quantities of surfactants. Those formulations
which have greater tolerance for salt usually contain major amounts
of acrylamide in the copolymers, and minor amounts of other
monomers. Unfortunately, acrylamide presents a health hazard in
manufacture and use of the copolymers, as well as environmental
problems. The difficulty of disposal of the solvents and large
amounts of free surfactants in the inverse emulsions has emphasized
the need for their replacement by compositions that do not cause
environmental pollution. This is especially true as regards
drilling fluids where soil polution is a problem, and in the drying
of coatings and adhesives where solvent evaporation contributes to
air pollution.
U.S. Pat. Nos. 3,657,175 discloses improved thickening agents based
on acrylics, styrene and butadiene, containing bound surfactant
groups.
As shown by U.S. Pat. Nos. 4,384,096; 4,351,754, and 4,421,903,
improved thickeners for aqueous systems have been developed in
which there are introduced to the acrylic polymer backbones ester
surfactant groups in sufficient number to enhance thickening and
rheological properties. These thickeners find use in paints,
coatings, adhesives, clearners, drilling fluids, textile printing
inks, personal care products, and the like. Difficulties
encountered in preparation of such copolymers are poor yield,
inadvertant prepolymerzation, dimerization of acrylic acid monomers
and the requirement of heat and vacuum conditions if complete
conversion is desired. These process steps are costly to carry out,
and invariably quantities of esterification catalyst and unreacted
nonionic surfactant remain in the product.
In preparing the product of U.S. Pat. No. 4,421,902 a statistical
mixture of acrylic acid dimer is obtained prior to esterification
which interferes with yield of the desired copolymer having
surfactant groups. In addition, the polymerization reaction not
being quantitative, produces varying results which is undesirable
in commercial practice.
A particular shortcoming of thickeners having an acrylic polymer or
copolymer backbone into which are incorporated ester surfactant
groups, is the tendency for the ester groups to hydrolize,
especially in the presence of highly alkaline compounds, such as
sodium hydroxide, whereby the thickening properties of the
copolymers is substantially diminished. Thus, such acrylic
copolymers do not lend themselves as effective thickeners for
aqueous systems containing excess alkali.
U.S. Pat. No. 4,514,552 discloses alkali-soluble thickeners for
latex paints which are emulsion copolymers of an alpha,
beta-monoethylenically unsaturated carboxylic acid, a
monoethylenically unsaturated monomer lacking surfactant capacity,
a nonionic urethane monomer which is a urethane reaction product of
a fatty alcohol or an alkyl phenol with a monoethylenically
unsaturated monoisocyanate, and a polyethlenically unsaturated
monomer which may be copolymerized with the copolymer. These
thickeners are said to provide superior thickening action and
superior hydrolytic stability as compared to the thickeners
containing ester groups.
SUMMARY OF THE INVENTION
According to this invention, new anionic copolymers are prepared by
emulsion copolymerizing (A) an addition copolymerizable nonionic
urethane monomer which is the urethane reaction product of a
monoethylenically unsaturated monoisocyanate with a polyhydric
alcohol or amine-containing nonionic surfactant of the formula
##STR1## where R, x and y are as indicated hereinbelow (B) an
.alpha.,.beta.-ethylenically unsaturated carboxylic acid monomer,
(C) a nonionic .alpha.,.beta.-ethylenically unsaturated monomer,
and (D) optionally a small amount of a polyethylenically
unsaturated cross-linking monomer. The emulsion polymerization is
carried out at a low pH and the resulting copolymers are
essentially water insoluble and are present in the aqueous reaction
medium in the form of a relatively stable dispersion. Upon addition
of an alkaline material to the dispersion to neutralize the
residual carboxyl groups on the copolymer, it becomes water soluble
and substantially thickens the aqueous system in which it is
present. The presence of the copolymerizable nonionic urethane
monomer imparts to the copolymer the ability to provide higher
water viscosities upon neturalization, as well as enhanced
electrolyte stability. This latter property is most important to
the stability of the rheological properties of thickened aqueous
systems of very high alkalinity. As noted above, where the
surfactant monomer contains ester linkages, hydrolysis of such
linkages is known to take place in the presence of highly alkaline
compounds, resulting in instability of systems thickened with
copolymers based on ester surfactant monomers. The copolymerizable
surfactant monomer can easily be prepared in near quantitative
yield without unwanted side reactions or formation of by-products
which would interfere with production of a commercial product of
uniform composition and properties. The reaction employed in
preparing the surfactant monomer is general for preparation of all
such monomers, and allows the tailoring of copolymers for specific
markets.
This invention also contemplates novel addition copolymerizable
polyhydric alcohol or amine-substituted carboxyl amino alkyl
acrylate surfactant monomers for use in preparing such anionic
copolymers.
The new copolymer thickeners are obtained by emulsion polymerizing
a monomer system comprising:
(A) about 1 to about 25 percent of at least one nonionic urethane
monomer which is the urethane reaction product of a
monoethylenically unsaturated monoisocyanate with a nonionic
surfactant of the formula: ##STR2## in which x is an integer of
from 1 to 150 and y is an integer of from 0 to 40 when R is a
sorbitan fatty ester of the formula ##STR3## where each of p, q, r
and s is an integer and the sum of said integers is from 0 to 100,
R.sub.1 is H or --COR.sub.2, and R.sub.2 is alkyl, alkylphenyl, or
dialkylphenyl having 5 to 30 carbon atoms; or x and y are each
integers of from 0 to 40 when R is --NH(CH.sub.2).sub.3 O--R.sub.3,
or ##STR4## where R.sub.2 is H or R.sub.3, and R.sub.3 is alkyl,
alkylphenyl, or dialkylphenyl of from 5 to 30 carbon atoms;
(B) about 5 to about 70 percent of a copolymerizable
.alpha.,.beta.-ethylenically unsaturated carboxylic acid monomer of
the formula ##STR5## where R is H and R.sub.1 is H, an alkyl group
containing from 1 to 4 carbon atoms, or --CH.sub.2 COOX; R is
--COOX and R.sub.1 is H, and X is H or an alkyl group containing
from 1 to 4 carbon atoms,
(C) about 10 to to about 90 percent of at least one nonionic,
copolymerizable .alpha.,.beta.-ethylenically unsaturated monomer of
the formula
where Y is H and Z is CN, CL, --COOR, --C.sub.6 H.sub.4 R, ##STR6##
or --CH.dbd.CH.sub.2 ; Y and Z are CL, and Y is CH.sub.3 and Z is
CN, ##STR7## --CH.dbd.CH.sub.2, --C.sub.6 H.sub.4 R, or
--COOR.sub.1, and R and H, CL, Br or alkyl containing from 1 to 4
carbon atoms; R.sub.1 is alkyl containing from 1 to 12 carbon
atoms, or hydroxyalkyl containing from 2 to 8 carbon atoms, and
R.sub.2 is alkyl containing from 1 to 8 carbon atoms; and
(D) up to 1 percent of a copolymerizable polyethylenically
unsaturated cross-linking monomer, said percentages being by
weight, based on the total weight of said monomers.
The copolymers are prepared by conventional emulsion polymerization
methods at low pH, e.g. pH 2.5-5, yielding a high solids, low
viscosity copolymer dispersion which thickens substantially upon
neutralization of at least some of the remaining carboxyl groups.
The copolymers are useful in a variety of applications,
particularly as thickeners for aqueous systems. As liquid emulsion
copolymers, they can readily be added at any point in the mixing
process. Alternatively, the copolymers can be dried by any one of
several well known methods, either as pure polymers, or onto a
solid substrate such a kaolin clay.
DETAILED DESCRIPTION OF THE INVENTION
MONOMERIC COMPONENTS
As noted previously the copolymers of this invention are prepared
by emulsion copolymerization of three essential types of monomers,
namely (A) a nonionic urethane monomer obtained by condensing a
nonionic polyhydric alcohol or amine-based surfactant with an
ethylenically unsaturated monoisocyanate, (B) an
.alpha.,.beta.-ethylenically unsaturated carboxylic acid monomer,
(C) a nonionic .alpha.,.beta.-ethylenically unsaturated monomer,
and (D) optionally a polyethyenically unsaturated cross-linking
monomer. The proportions of the monomers can be varied widely
within certain specific ranges to obtain thickening agents
possessing a variety of rheological properties. As prepared, the
aqueous acidic copolymer dispersions are easily handled high solids
latexes which upon neutralization of at least a portion of the
carboxyl groups, swell and thicken aqueous systems. The nonionic
urethane monomer serves as a major constitutent of the copolymer
backbone, and depending upon the amount thereof present permits
modification of the film forming characteristics of the copolymers
when dried. The bound urethane surfactant monomer permits
adjustment of the rheological properties provided by the copolymer,
decreases the electrolyte sensitivity and enhances the thickening
action of the copolymers.
(A) The nonionic urethane surfactant monomer.
According to preferred embodiments, the copolymers of this
invention comprise about 1 to about 25 weight percent, based on
total weight of monomers, of a polyhydric alcohol or
amine-substituted carbonyl amino alkyl acrylate of the formula:
##STR8## in which A is an alkylene group of the formula
(CH.sub.2).sub.n where n is an integer of from 2 to 20; Z is
CH.sub.2 .dbd.CH--, CH.sub.2 .dbd.C(CH.sub.3)--, CH.sub.2
.dbd.C(CL)--, CH.sub.3 CH.dbd.CH--, or ##STR9## x is an integer of
from 1 to 150 and y is an integer of from 0 to 40 when R is a
sorbitan fatty ester of the formula ##STR10## where each of p, q, r
and s is an integer and the sum of said integers is from 0 to 40,
R.sub.1 is H or --COR.sub.2, and R.sub.2 is alkyl, alkylphenyl, or
dialkylphenyl having 5 to 30 carbon atoms; or x and y are each
integers of from 0 to 40 when R is --NH(CH.sub.2).sub.3 O--R.sub.3,
or ##STR11## where R.sub.2 is H or R.sub.3, and R.sub.3 is alkyl,
alkylphenyl, or dialkylphenyl of from 5 to 30 carbon atoms;
The novel copolymerizable nonionic surfactant monomers of this
invention are prepared by the conventional condensation reaction of
an isocyanate with an active hydrogen compound (see High Polymers
XVI Part 1, pp. 71-74). The isocyanate compound can be prepared
using the method of U.S. Pat. No. 2,718,516 in which an amino
alcohol is first reacted with an alkyl chloroformate to produce a
compound of the formula
where A is an alkyl group. This compound is then reacted with an
acid halide of the formula
where X is a vinyl group such as CH.sub.2 .dbd.CH-- and X is
halogen, such as chlorine, to form the desired isocyanate. There is
also commercially available isocyanatoethyl methacrylate
manufactured by The Dow Chemical Company. Another commercially
available monoethylenically unsaturated monoisocyanate useful in
preparing the surfactant monomer (A) is alpha,
alpha-dimethyl-m-isopropenyl benzyl isocyanate (m-TMI, a product of
American Cyanamid Corp.).
In the preferred surfactant monomers A is an alkylene group
containing from 2 to 4 carbon atoms, x is an integer of from 2 to
20 and y is zero, and Z is either CH.sub.2 .dbd.CH-- or CH.sub.2
.dbd.C(CH.sub.3)--.
Examples of nonionic surfactants which can be reacted with the
monoethylenically unsaturated monoisocyanates to produce the novel
nonionic surfactant monomers of the invention are the sorbitan
fatty acid esters, such as sorbitan monooleate and sorbitan
monostearate, and the polyoxyethylene sorbitan fatty acid esters,
such as poly(oxyethylene).sub.20 sorbitan monolaurate and
poly(oxyethylene).sub.20 sorbitan monostearate. Suitable amine
surfactants include such primary amines as octyl amine and dodecyl
amine, and such secondary amines as dipentyl and diheptyl amine.
These reactants for the most part are commercially available.
Moisture should be removed before use thereof since water
interferes with the isocyanate reaction. By employing a suitable
stannous catalyst, the condensation reaction is carried out at
relatively low temperature, e.g. 40.degree. C. to 60.degree. C. and
essentially quantitative yields are obtained. No by-products are
formed, and thus purification of the product is unnecessary. This
feature of the reaction is important in determining and controlling
the amount of bound surfactant monomer present in the emulsion
copolymer, whereby copolymer reproducability is readily
accomplished.
Preferably the surfactant monomer comprises from about 5 to 15
percent by weight of the copolymer, 7 to 10 percent being a
particularly preferred quantity for such monomer.
(B) The copolymerizable .alpha.,.beta.-ethylenically unsaturated
carboxylic acid monomer.
The copolymerizable .alpha.,.beta.-ethylenically unsaturated
carboxylic acid monomers have the general formula ##STR12## where R
is H and R.sub.1 is H, an alkyl group containing from 1 to 4 carbon
atoms, or --CH.sub.2 COOX; R is --COOX and R.sub.1 is H, and X is H
or an alkyl group containing from 1 to 4 carbon atoms,
Examples of these acid monomers include such monobasic acids as
acrylic, methacrylic, crotonic, and acyloxypropionic acid. Dibasic
acid monomers include maleic, fumaric, and itaconic acid, and they
can be used in place of a portion, e.g. up to about 10 weight
percent, of the monobasic acid. Monomers which are monoesters of
dibasic acids, such as the monobutyl ester of maleic acid can also
be used to advantage. The weight percent of carboxylic acid monomer
is preferably between 5 and 70 percent, based on the total weight
of monomers present. More preferably between 30 to 50 weight
percent of the acid monomer is present. The most preferred weight
percentage of the carboxylic acid monomer is between 35 and 45
percent. Acrylic and methacrylic acid are preferred acid
monomers.
(C) Nonionic .alpha.,.beta.-ethylenically unsaturated monomers.
In the copolymers of this invention a monomer which serves as a
major component of the backbone is a nonionic copoymerizable
.alpha.,.beta.-ethyenically unsaturated monomer of the formula:
where Y is H and Z is CN, CL, --COOR, --C.sub.6 H.sub.4 R,
##STR13## or --CH.dbd.CH.sub.2 ; Y and Z are CL, and Y is CH.sub.3
and Z is CN, ##STR14## --CH.dbd.CH.sub.2, --C.sub.6 H.sub.4 R, or
--COOR.sub.1, and R is H, CL, Br or alkyl containing from 1 to 4
carbon atoms; R.sub.1 is alkyl containing from 1 to 12 carbon
atoms, or hydroxyalkyl containing from 2 to 8 carbon atoms, and
R.sub.2 is alkyl containing from 1 to 8 carbon atoms.
Examples of these nonionic monomers are the C.sub.1 -C.sub.8 alkyl
and C.sub.2 -C.sub.8 hydroxyalkyl esters of acrylic and methacrylic
acids such as methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate,
butyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl
methacrylate, 2-hydroxypropyl methacrylate, styrene, butadiene,
isoprene, vinyl chloride, vinylidene chloride, acrylonitrile,
methacrylonitrile, vinyl acetate, vinyl butyrate, vinyl caprolate,
p-chloro styrene, isopropyl styrene, vinyl toluene and the like.
The preferred monomers are acrylate and methacrylate esters alone
or mixtures thereof with styrene, acrylonitrile, or vinyl
acetate.
The nonionic monomer generally comprises from about 10 to about 90
percent by weight of the copolymer. The preferred proportion of
this monomer is 30-70 weight percent, while the most preferred
range is about 50-60 weight percent.
(D) The optional polyethylenically unsaturated cross-linking
monomer.
A small amount of a polyethylenically unsaturated monomer may be
added as a cross-linking agent. Such monomers include diallyl
phthalate, vinyl crotonate, allyl methacrylate, divinyl benzene,
NN.sup.1 -methylene-bis-acrylamide, ethylene glycol diacrylate,
ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and the
like. Preferably from about 0.05 to 1 weight percent, based on
total monomers, of the polyethylenically unsaturated monomer is
incorporated into the copolymer.
The Copolymerization Reaction
The copolymers of this invention are readily prepared by
conventional emulsion polymerization techniques using the monomers
described above. The polymerization can be carried out in
continuous, semi-continuous or batch fashion. The polymerization
reaction can be initiated at 40.degree.-90.degree. C., preferably
75.degree.-85.degree. C., with the usual thermal decomposition
initiators such as ammonium persulfate or potassium persulfate or
at lower temperatures using redox initiators such as t-butyl
hydroperoxide/bisulfite, or hydrogen peroxide with a ferrous
compound. Alternatively azo initiators such as
azobisisovaleronitrile can be used.
An anionic emulsifier is normally included in the reaction medium
at a concentration of about 1 to 3 percent to maintain the
copolymer product in the form of a stable aqueous dispersion.
Suitable emulsifiers for such purpose are sodium lauryl sulfate,
sodium dodecylbenzene sulfonate, as well as other ammonium, and
alkali metal alkyl aryl sulfonates, ammonium and alkali metal alkyl
sulfates, sodium dioctyl sulfosuccinate, and sulfonated alkyl
esters and amides. Optionally, a nonionic surfactant, such as
nonylphenol ethoxylates, octylphenol ethoxylates and linear or
branched alkyl ethoxylates also may be employed if desired as they
have a marked effect on the properties of the copolymer
product.
The polymerization is carried out at a pH below about 5.0,
generally in the range of 2.5 to 5, to maintain the insolubility of
the copolymer in the continuous water phase by reason of the
presence of free carboxyl groups. The finished copolymer
dispersions have a relatively low viscosity even at a solids
content of from 20-40 weight percent, or higher. Upon addition of
an alkali to neutralize at least a portion of the free carboxyl
groups, aqueous systems containing the copolymers markedly
thicken.
The Properties of the Copolymers
The improved copolymers of this invention are in-situ thickeners
prepared by emulsion copolymerization at a pH between 2.5 and 5.
The polymerization product is a milky white latex-like aqueous
dispersion having a solids content up to about 50 percent,
generally from 20-40 percent, by weight. The viscosity of these
dispersions is generally low, typically from 25-100 cps at
25.degree. C. The dispersions, which are relatively stable, are
easily blended into a variety of aqueous systems. Different
dispersions according to the invention can be blended together to
provide the properties desired for a specific application. The pure
copolymer, in dried form, is a solid at a temperature of 25.degree.
C.
Upon addition of an alkaline material such as an alkali metal
hydroxide, sodium carbonate, or other bases such as ammonium
hydroxide, methylamine or diethylamine, at least some of the free
carboxy groups in the polymer are neutralized, rendering the
copolymer soluble in water. At a low pH, e.g. a pH below about 5.5,
the polymer exists in the form of discrete, water insoluble
particles, having an average particle size of about 0.1 to 5
microns. Average molecular weights of the copolymers are estimated
to be between about 100,000 and 5,000,000. Preferred copolymers
have an average molecular weight of from about 500,000 to
1,000,000. Copolymers having substantially higher molecular weights
may be obtained when a polyethylenically unsaturated cross-linking
monomer is also present.
The selection of the nonionic .alpha.,.beta.-ethylenically
unsaturated monomer has a significant effect on the thickening
potential of the copolymers. Other properties such as the rheology
of thickened compositions are dependent on the pH of
neutralization, and the glass transition temperature, which
properties may also be modified by the choice of non-ionic monomer.
For example, butyl acrylate can be incorporated into the copolymer
backbone to lower the glass transition temperature, or "soften" the
copolymer. On the other hand, incorporation of methacrylate esters
into the copolymer will stiffen the copolymer backbone and thereby
harden a cast film of the polymer.
The following examples, in which all parts are by weight unless
otherwise indicated, are presented as a means of further describing
the preparation and use of the novel copolymers of this invention,
and should not be considered as limiting the scope of the
invention.
EXAMPLE 1
Preparation of 3-methoxy propyl-1 amino carbonyl amino ethyl
methacrylate.
A mixture of 100 grams of previously dried 1-amino-3-methoxy
propane (0.660 mole) and 0.5 grams of monomethyl ether of
hydroquinone (MEHQ) was charged to a 500 ml reaction flask equipped
with a thermometer, mechanical stirrer, heating mantle, condenser,
and drying tube. The mixture was heated to 45.degree. C. and 0.3
grams of stannous octoate were added. To this mixture were added
100.3 grams of 2-isocyanato ethyl methacrylate (0.647 mole) via a
dropping funnel over 75 minutes while maintaining the temperature
of the mixture between 45.degree.-50.degree. C. When the addition
of the isocyanate was complete, the mixture was held at 50.degree.
C. for 1 hour to ensure complete reaction of the isocyanate. The
product after cooling was a yellow oil which could be used in
copolymer synthesis without purification. The reaction conditions
described above apply generally for synthesizing surfactant
monomers by reaction between isocyanate and primary or secondary
amines.
EXAMPLE 2
Preparation of the sorbitan monooleate poly (oxyethylene).sub.19
ethyl oxycarbonyl amino ethyl methacrylate.
A mixture of 100 grams of previously dried poly(oxyethylene).sub.20
sorbitan mono-oleate (0.0765 mol) and 0.25 grams of MEHQ were
charged to a 500 ml reaction flask equipped with a thermometer,
mechanical stirrer, heating mantle, condenser, and drying tube. The
mixture was heated to 45.degree. C., and 0.25 grams of stannous
octoate and 8.89 of 2-isocyanato ethyl methacrylate (0.0573 mol)
were added while holding the reaction temperature at 45.degree. C.
When the addition of isocyanate was complete the mixture was held
at 45.degree. C. for 75 minutes. The product after cooling was a
yellow liquid. The reaction conditions described in this example
apply to the reacton between isocyanate and both ethoxylated and
non-ethoxylated sorbitan ester surfactants.
EXAMPLE 3
Preparation of sorbitan monostearate poly(oxyethylene).sub.19 ethyl
oxycarbonyl amino ethyl methacrylate.
A mixture of 200 grams of previously dried poly(oxyethylene).sub.20
sorbitan monostearate (0.153 mole) and 0.5 grams of MEHQ were
charged to a reactor as described in Example 1. The mixture was
heated to 45.degree. C., and 0.25 grams of stannous octoate were
added. While holding the reaction temperature at
45.degree.-50.degree. C. 17.76 grams of 2-isocyanato ethyl
methacrylate (0.114 mole) were added via a dropping funnel over 1
hour. When the additon of isocyanate was complete the mixture was
held at 45.degree. C. for 75 minutes. Upon cooling the product was
a yellow liquid which could be used without purification.
In Table I, below, the surfactants reacted with 2-isocyanato ethyl
methacrylate and the procedure used, as designated by the
appropriate example number, are set forth:
TABLE I ______________________________________ CPS* Surfactant
Reactant Example No. ______________________________________ 1
1-amino-3-oxomethane 1 2 1-amino-3-oxo-n-octane (CAS-68511411) 1 3
1-amino-3-oxo-n-tetradecane 1 4 Monooleyl amine 3 5 Sorbitan
monostearate 3 6 Poly(oxytheylene).sub.20 sorbitan monolaurate 3 7
Poly(oxyethylene).sub.20 sorbitan monostearate 3 8
Poly(oxyethylene).sub.20 sorbitan monooleate 3
______________________________________ *"CPS" stands for "copolymer
surfactant monomer
EXAMPLE 4
Preparation of a copolymer comprising heptadecylcarbonyloxy
poly(oxyethylene).sub.19 ethyloxycarbonyl amino ethyl methacrylate,
methacrylic acid and ethyl acrylate.
An aqueous monomer mixture was prepared by combining 6.14 grams of
a 30% solution of sodium lauryl sulfate, 23 grams of
heptadecylcarbonyloxy poly(oxyethylene).sub.19 sorbitan, and 264
grams of water. After the monomer was well dispersed in the water,
92.0 grams of methacrylic acid, 115.0 grams ethyl acrylate, and
0.23 grams diallyl phthalate were added and the mixture was
vigorously agitated to provide a uniform white emulsion. To an all
glass reaction vessel equipped with a mechanical stirrer, heating
mantle, thermometer, condenser, and dropping funnel were added 200
grams of water and 6.14 grams of a 30% solution of sodium lauryl
sulfate. The reactor contents were heated with agitation to
85.degree. C. and 9.9 grams of 2.5% ammonium persulfate solution
were added. Addition of the monomer pre-emulsion mixture was begun
at the rate of 2.5 ml./min. After 10 minutes the monomer feed rate
was increased to 8 ml./min. and 2.5 ml. shots of 0.35% ammonium
persulfate were added at 5 minute intervals. After completion of
the monomer addition, 19.8 grams of 0.45% ammonium persulfate
solution were added and the copolymer was cooked out for 1.5 hours.
The resulting emulsion copolymer was cooled and filtered through a
40 mesh screen to remove any grit. The filtrate had a 30% solids
content and the pH thereof was 2.9. A 1.0% solids solution thereof
raised to pH 9.0 with NaOH, provided a viscosity of 10,000 cps at
25.degree. C. (#6 spindle at 20 RPM Brookfield LVT).
Using the above-described emulsion polymerization procedures, nine
(9) different copolymer dispersions of the invention were prepared
and these are identified by "LEC" (liquid emulsion copolymer)
numbers in Table II, below. Also presented in this table are
viscosities for aqueous systems containing the copolymers. In two
of the three systems tested either sodium or calcium chloride was
present, while the third merely contained water.
TABLE II
__________________________________________________________________________
LIQUID EMULSION COPOLYMERS (LEC) Brookfield Viscosity (CPS at
25.degree. C.) Monomer CPS Copolymer Concentration 3% Copolymer
Concentration LEC Weight % (1) NO. (2) 1% (3) 2% (3) 3% (3) 2%
Sodium Chloride (3)
__________________________________________________________________________
1 55.0/40.0/5.0 1 2,000 3,700 6,500 3,800 2 55.0/40.0/5.0 2 2,100
6,000 17,000 9,500 3 50.0/40.0/10.0 2 2,000 14,000 39,500 17,500 4
55.0/40/0/5/0 3 2,000 20,000 62,500 26,000 5 50.0/40.0/10.0 6 5,000
30,500 56,500 22,000 6 45.0/40.0/15.0 6 10,000 54,500 .sup. 128,000
(4) 26,000 7 50.0/40.0/10.0 7 9,500 62,000 .sup. 148,000 (4) 34,400
8 49.0/40.0/11.0 8 6,000 45,000 .sup. 120,000 (4) 6,000 9
55.0/40.0/5.0 8 7,500 28,000 39,500 17,500
__________________________________________________________________________
(1) In all examples proportions are for ethylacrylate/methacrylic
acid/CPS. All copolymers include 0.1% diallylphthalate. (2)
Examples from Table I. (3) Spindle #6 @ 10 RPM Brookfield RVT. (4)
Spindle #7 @ 10 RPM Brookfield RVT.
Description of Uses of the Copolymers
As noted previously the copolymers of this invention are prepared
by conventional emulsion polymerization methods and the resulting
copolymer dispersions which contain 5 to 50 percent, generally 20
to 40 percent of copolymer, are suitable as is for use in various
industrial applications such as adhesives, coatings, drilling
fluids, cleaners, walljoint compounds, lotions and other personal
care products, highly absorbant applications, paints, wall paper
adhesives, textile print pastes, textile sizings, oil recovery
applications, and the like.
Freeze point depressants may be added to the latex products of this
invention to provide moderate cold weather protection during
shipping if desired. The list of suitable freeze point depressants
is long and the members thereof are well known to trade. Among the
generally suitable freeze point depressants are lower molecular
weight alcohols and glycols such as methanol, ethanol, isopropanol,
butanol, ethylene glycol, propylene glycol, butylene glycol,
diethylene glycol, ethylene glycol monoethylether, ethylene glycol
dimethyl ether, and the like.
Alternatively, the product of the invention can be dried by a
variety of known industrially available methods. These include, but
are not limited to, tray drying, spray drying, drum drying, freeze
drying, and precipitation and recovery followed by tray or
fluidized bed drying. Additionally, the copolymer products of this
invention can be dried onto a variety of particulate substrates
such as silica, kaolin, lignite, bentonite and other clays, and
weighting materials normally utilized in various applications. The
purpose of using such substrates is to enable delivery of dry
products capable of rapid mixing and dispersion in various
applications where the support material is compatable with the
desired composition. In addition, the presence of a solid
particulate support facilitiates the drying of copolymers that form
films at relatively low temperatures, frequently a limiting factor
in drying process selection. The use of dried blends of this type
eliminates all concern of product freeze damage and related costs
to provide cold weather protection during shipping. In addition,
copolymer products of various properties can be delivered to the
end user in dry form with acceptable economics.
The copolymer dispersions of the invention usually can be combined
in aqueous compositions designed for partular applications with
predictable effects due to the fact that the surfactant monomer may
be carefully chosen and incorporated in the copolymer chain in the
desired amount.
Print Pastes
The copolymer dispersions of the invention are of interest as print
paste thickeners for use in, but not limited to, textile printing.
For example, aqueous dispersions having a concentration of 1
percent polymer solids of several of the foregoing examples were
studied in "clear" formulations resulting from neutralization with
ammonium hydroxide to pH 9. The "clear" formulations were then
typically treated with up to 10% of an acrylic "low crock" print
binder, a representative composition of such type being offered for
sale by Alco Chemical Corporation under the designation PB-1, a 45%
solids acrylic emulsion polymer (CAS No. 27082-10-6) and 5% of a
color concentrate of the type sold by many companies to textile
mills. A typical product of the general type is offered for sale by
Catawba Charlabs of North Carolina as Impriment Blue SGG, a blue
paste for test purposes.
Viscosity determinations were made on the "clear" formulations and
print pastes and the results are set forth in Table III, below. The
"LEC" numbers which appear in this table are for copolymers of the
same number identified in Table II above.
TABLE III ______________________________________ Brookfield
Viscosity (cps @ 25.degree. C.) 10 RPM LEC Clear Dispersion 1%
Solids Print Paste ______________________________________ 1 5,000
3,000 ______________________________________
Any number of different color concentrates may be substituted for
the blue concentrate used in these examples. Colors are selected to
answer the need of stylists in the printing industry. The degree of
crosslinking of the copolymer thickeners can be varied for the
purpose of altering print paste rheology. The viscosities set forth
in Table III can be varied by addition of a nonionic surfactant to
the print paste.
Adhesive Applications
General purpose adhesives may be thickened wth copolymer
dispersions of this invention to the high viscosity required for
rendering the adhesives useful for various purposes such as floor
tile and carpet installation. For example, there is commercially
available for such purposes an adhesive having the necessary filler
loading and containing a solvent-based tackifying resin, to which a
styrene butadiene latex is added. A small amount of the dispersion
was added to the adhesive and Brookfield viscosities were
determined on the adhesive before and after addition of the latex.
The results obtained are set forth in Table IV, below:
TABLE IV ______________________________________ Brookfield
Viscosity @ 5 RPM (cps @ 25.degree. C.)* Wet Parts LEC Used**
Adhesive Base After Latex Addition
______________________________________ 1 0.67 24,000 21,000 --
15,000 -- ______________________________________ *Determined with a
Heliopath TC viscometer. **30% solids, see Table II
Oil Well Drilling Fluids
Typical oil well drilling fluids were prepared using standard
methods, and the fluids were subjected to the API Fluid Loss Test
and Fann 35 Viscosimeter test. A comparison was made of the
thickening effects of various thickeners of this invention
utilizing a standard bentonite composition (Aquagel.RTM. of N. L.
Baroid, Inc.) dispersed in mud at 15 pounds per barrel (PPB). In
some of the tests fresh water mud was used. In addition, muds
contaminated with either sodium chloride at a concentration of
25,000 mg/l (PPM) or 2000 mg./l (PPM) of calcium chloride were also
tested for thickening effect. The muds were tested for apparent
viscosity at 600 RPM (A.V.), plastic viscosity in cps. (P.V.),
yield point (Y.P.), lbs/100 ft..sup.2, gel stength and fluid loss
(F.L.) API Filtrate (RP 13B Fluid Loss) at 0.25 PPB active
copolymer addition. The results are set forth in Tables V, VI and
VII, below:
TABLE V ______________________________________ Fresh Water System
10 sec./ Apparent Viscosity (cps)* 10 Gel LEC 3 6 100 200 300 600
min. P.V. Y.P. F.L. ______________________________________ 1 18 20
36 47 54 71 20/ 17 37 14.5 27 Base 1 1 6 9 11 19 1/4 8 3 17.0
______________________________________ *Fann 35 Viscometer, reading
divided by two.
TABLE VI ______________________________________ 25,000 ppm Sodium
Chloride System 10 sec./ Apparent Viscosity (cps)* 10 Gel LEC 3 6
100 200 300 600 min. P.V. Y.P. F.L.
______________________________________ 1 11 11 15 18 20 28 13/ 8 12
28.0 14 Base 10 13 17 19 22 26 15/ 4 18 22.0 16
______________________________________ *Fann 35 Viscometer, reading
divided by two.
TABLE VII ______________________________________ 2000 PPM Calcium
Chloride System 10 sec./ Apparent Viscosity (cps)* 10 Gel LEC 3 6
100 200 300 600 min. P.V. Y.P. F.L.
______________________________________ 1 8 10 11 16 19 21 9/9 2 17
77.0 Base 8 10 14 16 18 20 10/ 4 14 70.0 12
______________________________________ *Fann 35 Viscometer, reading
divided by two.
To illustrate the above, Standard Procedure for Testing Drilling
Fluids, API RP13B, Seventh Edition, 1978, is employed.
Walljoint Compound
A walljoint compound was prepared in which were included various
copolymer dispersions of the invention. This compound, designed for
use in gypsum board tape joints for building construction, had the
formulation set forth in Table VIII.
TABLE VIII ______________________________________ Walljoint
Compound ______________________________________ Part A Component
Parts by Weight ______________________________________ Water 600
Dispersant 10 LEC thickener of (See Table II) the invention Clay 20
Ethylene glycol 10 Defoamer 10 Latex 89
______________________________________ Part B Component Weight
Percent ______________________________________ Titanium dioxide 494
Mica (325 mesh) 175 Filler 175
______________________________________
Procedure
The components of Part A were blended together to provide a smooth
mixture using a low shear folding type mixer. The components of
Part B were dry blended and added slowly to Part A, and mixing was
continued until a smooth blend was obtained. Part of the water of
Part A was withheld and added during the addition of Part B.
The resulting walljoint compounds of this invention were tested for
certain physical properties and the results are tabulated in Table
IX, below:
TABLE IX ______________________________________ Brookfield
Viscosity (cps @ 25.degree. C.) 2.5 RPM Spindle TE, Non Water LEC*
Heliopath Viscometer Leveling Slip Retention
______________________________________ 1 2,000,000 Good Good Good
Blank 600,000 Poor Poor Poor ______________________________________
*See Table II
Paper Coatings
Paper coatings prepared using copolymers of this invention offer an
improvement over prior coatings containing thickeners, especially
as regards efficiency, i.e. the amount of thickener required to
increase the viscosity of the coatings to useful levels. In this
regard, the overall rheology of coatings of both the low and high
shear type containing thickeners of this invention were studied.
The fluid retention of the coatings was compared using an "S. D.
Warren" tester, and electronic water retention (EWR) in seconds was
measured. The EWR values have a bearing on the overall usefulness
of a particular thickener, regardless of the amount used in the
coating, and provides evidence of the runability of the coating.
The results of the tests are presented in Tables X and XI.
TABLE X
__________________________________________________________________________
Viscosity, 3000 cps @ 25.degree. C. Weight Percent Thickener
Brookfield Fluid Retention Kaltec*** Dry Polymer Parts by
Viscosity-20 RPM EWR, Sec. High Shear on 100 Parts LEC** Weight
(Dry) (cps @ 25.degree. C.) 30#/ream #5 Whatman Viscosity, cm.
Coating Clay
__________________________________________________________________________
Paper Coating Formulation* 1 0.2 1100 23 54 5.1 0.55 0.4 2300 0.6
4000 0.8 -- Control (no thickener) 100 6 22 NR -- Paper Coating
Formulation.sup.+ 1 0.2 100 28 63 8.9 1.1 0.4 500 0.6 1000 0.8 2100
Control (no thickener) 100 6 22 NR --
__________________________________________________________________________
*Dow 620 butadienestryene latex 15.0 dry parts, number one coating
clay 100 parts solids, 50% coating solids, pH 9.0 by addition of
ammonium hydroxide. .sup.+ National Starch Company polyvinyl
acetate latex No. 1105 15.0 dry parts, number one coating clay 100
solid parts, 50% solid coating, pH 9.0 by addition of ammonium
hydroxide. **See Table II ***"E" Bob, 4400 rpm; 200,000 spring
set.
* * * * *